CN118006025A - Marine photovoltaic cable insulation sheath material and preparation method thereof - Google Patents
Marine photovoltaic cable insulation sheath material and preparation method thereof Download PDFInfo
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- CN118006025A CN118006025A CN202410417277.8A CN202410417277A CN118006025A CN 118006025 A CN118006025 A CN 118006025A CN 202410417277 A CN202410417277 A CN 202410417277A CN 118006025 A CN118006025 A CN 118006025A
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- ethylene propylene
- diene monomer
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000009413 insulation Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 85
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 77
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003063 flame retardant Substances 0.000 claims abstract description 31
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004611 light stabiliser Substances 0.000 claims abstract description 20
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 15
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
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- 239000002131 composite material Substances 0.000 claims abstract description 4
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- 238000003756 stirring Methods 0.000 claims description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 21
- -1 polyethylene Polymers 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 14
- 229910000077 silane Inorganic materials 0.000 claims description 14
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 6
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 6
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- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 12
- 239000007921 spray Substances 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 7
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- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 229920006253 high performance fiber Polymers 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
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- 239000004593 Epoxy Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of photovoltaic cables, and discloses an offshore photovoltaic cable insulation sheath material which comprises the following raw materials in parts by weight: 50-70 parts of high-density polyethylene, 10-25 parts of modified ethylene propylene diene monomer, 5-15 parts of modified basalt fiber, 1-1.5 parts of lubricant, 0.5-2 parts of antioxidant and 0.05-0.5 part of light stabilizer; the modified ethylene propylene diene monomer is an epoxidized ethylene propylene diene monomer grafted (4-tolyl) phenyl phosphorus oxide flame retardant modified ethylene propylene diene monomer; the modified basalt fiber is gamma-aminopropyl triethoxysilane and nano titanium dioxide composite modified basalt fiber, the mechanical property and the flame retardant property of the insulating sheath material are enhanced by adding the modified ethylene propylene diene monomer, and meanwhile, the salt spray resistance and the mechanical property of the insulating sheath material are improved by adding the modified basalt fiber.
Description
Technical Field
The invention belongs to the technical field of photovoltaic cables, and particularly relates to an offshore photovoltaic cable insulation sheath material and a preparation method thereof.
Background
At present, along with the exhaustion of fossil energy, development emphasis is transferred to novel renewable energy sources in various countries, development of a photovoltaic solar system has been rapidly progressed in recent years, a photovoltaic power station is used for converting solar energy into electric energy, a photovoltaic cable is used for transmitting the converted electric energy, and the photovoltaic cable is one of important components in a photovoltaic industry chain and has very wide application in the field of photovoltaic power generation.
When the photovoltaic cable is used at sea, larger pressure is required to be borne, damage and salt spray corrosion can occur after the photovoltaic cable is used for a long time, polyolefin is selected as an insulating sheath material of the existing photovoltaic cable at sea, the polyethylene cable material has very wide application in the field of the photovoltaic cable, but the salt spray resistance, the pressure resistance and the flame retardance are poor, a large amount of flame retardant is added for realizing the flame retardance in the preparation process of the existing insulating sheath material, the mechanical property of the insulating sheath can be influenced by the addition of the large amount of flame retardant, and the application of the insulating sheath material of the photovoltaic cable at sea is further limited.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide the offshore photovoltaic cable insulation sheath material and the preparation method thereof, wherein the mechanical property and the flame retardant property of the insulation sheath material are enhanced by adding the modified ethylene propylene diene monomer, and the salt spray resistance and the mechanical property of the insulation sheath material are further improved by adding the modified basalt fiber.
The aim of the invention can be achieved by the following technical scheme:
the marine photovoltaic cable insulation sheath material comprises the following raw materials in parts by weight: 50-70 parts of high-density polyethylene, 10-25 parts of modified ethylene propylene diene monomer, 5-15 parts of modified basalt fiber, 1-1.5 parts of lubricant, 0.5-2 parts of antioxidant and 0.05-0.5 part of light stabilizer;
The modified ethylene propylene diene monomer is an epoxidized ethylene propylene diene monomer grafted (4-tolyl) phenyl phosphorus oxide flame retardant modified ethylene propylene diene monomer; the modified basalt fiber is a gamma-aminopropyl triethoxysilane and nano titanium dioxide composite modified basalt fiber.
Preferably, the lubricant is a polyethylene wax or an oxidized polyethylene wax; the antioxidant is one of an antioxidant 1010, an antioxidant 1076 and an antioxidant 168; the light stabilizer is one of a light stabilizer 2020, a light stabilizer 770 and a light stabilizer 944.
Preferably, the preparation method of the modified ethylene propylene diene monomer comprises the following steps:
A. Adding ethylene propylene diene monomer into a toluene solvent, placing the ethylene propylene diene monomer into a water bath kettle at 40-60 ℃, stirring the mixture until the ethylene propylene diene monomer is completely dissolved, adding a formic acid aqueous solution, controlling the temperature of the water bath kettle to be 15-35 ℃, continuously adding tert-butyl hydroperoxide, raising the temperature in the water bath kettle to 70-90 ℃, reacting for 4-12 hours, cooling the product, precipitating, washing and drying to obtain the epoxidized ethylene propylene diene monomer;
B. Adding toluene and anhydrous aluminum chloride into phenyl phosphorus dichloride, heating to 65-80 ℃ for reaction for 10-12 hours, cooling reactants to room temperature, adding 10wt% hydrochloric acid and benzene for hydrolysis, separating an organic layer, extracting a water layer by using benzene, merging the organic layers, washing by using deionized water, and evaporating the organic solvent under reduced pressure to obtain the (4-tolyl) phenyl phosphorus oxide flame retardant;
C. And adding a dimethylbenzene solvent into the epoxidized ethylene propylene diene monomer, fully dissolving, adding a (4-tolyl) phenyl phosphorus oxide flame retardant, heating to 110-135 ℃, stirring for 8-12 hours, performing rotary evaporation to remove dimethylbenzene after the reaction is finished, and performing vacuum drying to obtain the modified ethylene propylene diene monomer.
Preferably, the addition ratio of ethylene propylene diene monomer, formic acid aqueous solution and tert-butyl hydroperoxide in the step A is 5g: 1-2.5 mL: 2-5 mL.
Preferably, the mass ratio of the phenyl phosphorus dichloride to the toluene in the step B is 8g: 5-10 mL.
Preferably, the mass ratio of the epoxidized ethylene propylene diene monomer to the (4-tolyl) phenyl phosphorus oxide flame retardant in the step C is 5g: 3-8 g.
Preferably, the preparation method of the modified basalt fiber comprises the following steps:
(1) Soaking basalt fibers in an acetone solution for 10-12 hours, taking out and draining, then soaking and washing the basalt fibers in a container filled with deionized water, filtering out the basalt fibers after repeated for a plurality of times, and then drying the basalt fibers in an oven to obtain pretreated basalt fibers;
(2) Adding deionized water into nano titanium dioxide, stirring and mixing at room temperature, performing ultrasonic dispersion, adding sodium chloroacetate, dropwise adding sodium hydroxide solution to adjust the pH to 11-13, heating in an oil bath at 100-120 ℃ for 3-5 h, cooling to room temperature, repeatedly washing with deionized water until the pH is neutral, and performing centrifugal separation and drying to obtain carboxylated nano titanium dioxide;
(3) And (3) taking absolute ethyl alcohol, deionized water and gamma-aminopropyl triethoxysilane, hydrolyzing at 45-60 ℃ to obtain silane hydrolysate, adding pretreated basalt fiber and carboxylated nano titanium dioxide into the silane hydrolysate, keeping the temperature at 45-55 ℃ and stirring for 30-60 min, and drying in an oven after the reaction is finished to obtain the modified basalt fiber.
Preferably, in the step (2), the mass ratio of the nano titanium dioxide to the sodium chloroacetate is 1: 1.2-1.5.
Preferably, the volume ratio of the absolute ethyl alcohol, deionized water and gamma-aminopropyl triethoxysilane in the silane hydrolysate in the step (3) is 3-4: 6-7: 90, the mass ratio of the silane hydrolysate to the pretreated basalt fiber to the carboxylated nano titanium dioxide is 10:3:0.05 to 0.15.
Preferably, the preparation method of the offshore photovoltaic cable insulation sheath material comprises the following steps: weighing the raw materials according to parts by weight, adding the high-density polyethylene, the modified ethylene propylene diene monomer, the modified basalt fiber and the lubricant into a mixer, stirring and mixing, wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 15-20 min, then adding the light stabilizer and the antioxidant, continuously stirring and mixing, and at the moment, the temperature of the mixer is set to be 70-80 ℃ and the stirring time is 30-40 min to obtain a mixture, and putting the mixture into a double-screw extruder for extrusion molding to obtain the insulating sheath material.
The invention has the beneficial effects that:
According to the invention, formic acid is used as a catalyst, tert-butyl hydroperoxide is used as an oxidant, ethylene propylene diene monomer is catalyzed to be epoxidized, and epoxy ethylene propylene diene monomer is obtained, in addition, phenyl phosphine dichloride reacts with toluene to prepare the (4-tolyl) phenyl phosphorus oxide flame retardant, epoxy groups in the structure of the epoxy ethylene propylene diene monomer can be subjected to ring opening addition reaction with P-H bonds in the structure of the (4-tolyl) phenyl phosphorus oxide flame retardant under the high temperature condition, the (4-tolyl) phenyl phosphorus oxide flame retardant is further chemically connected in an ethylene propylene diene monomer molecular chain, so that the modified ethylene propylene diene monomer is obtained, meanwhile, a large amount of oxygen acids of phosphorus can be generated after the (4-tolyl) phenyl phosphorus oxide is combusted, the oxygen acids of phosphorus can rapidly catalyze ethylene propylene diene monomer molecules to form a compact carbon protection layer and are adhered to the surface of high-density polyethylene, the high-density polyethylene is protected, the high-density polyethylene is prevented from being further combusted, a good flame retardant effect is achieved, the problem of migration and exudation is avoided, the insulation sheath material achieves a long-term flame retardant effect, and the ethylene propylene diene monomer has good reinforcing and toughening effect, and the comprehensive properties such as tensile strength and impact strength of the insulation sheath material can be obtained.
According to the invention, the salt spray resistance of the insulating sheath material is improved by adding the modified basalt fiber, the basalt fiber is an inorganic environment-friendly high-performance fiber material, the inorganic environment-friendly high-performance fiber material has the characteristics of high elastic modulus, high tensile strength, high wear resistance, excellent high temperature resistance, acid and alkali resistance and the like, the basalt fiber is modified by the silane coupling agent and the carboxylated nano titanium dioxide, the amino group at one end of the silane coupling agent and the carboxylated nano titanium dioxide undergo amidation reaction, the silicon hydroxyl group generated by hydrolysis at the other end of the silane coupling agent and the hydroxyl group on the surface of the pretreated basalt fiber undergo condensation reaction, the nano titanium dioxide is an important inorganic ultraviolet shielding agent, the ultraviolet ageing can be reduced, the inorganic environment-friendly high-performance fiber material has the effects of spectral antibiosis, deodorization, mildew resistance and the like, the carboxylated nano titanium dioxide is grafted on the surface of the basalt fiber through the silane coupling agent, the dispersion of the nano titanium dioxide is facilitated, the existence of nano particles increases the roughness of the surface of the basalt fiber, the porosity of the composite material is reduced, the mechanical biting force and chemical bonding force of the basalt fiber and a matrix are increased, the interfacial bonding strength is increased, the invasion of salt spray resistance and the salt spray resistance of the insulating sheath material is further improved, and the modified basalt fiber is used as the insulating sheath material with excellent mechanical property.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Basalt fiber in the examples and comparative examples of the invention is produced by Shenzhen, teli New Material technology Co., ltd., 3mm in length and 13 μm in diameter.
The preparation method of the modified ethylene propylene diene monomer rubber in the embodiment 1 comprises the following steps:
A. Adding 5g ethylene propylene diene monomer into 150mL toluene solvent, placing in a water bath kettle at 40 ℃, stirring until the ethylene propylene diene monomer is completely dissolved, adding 1mL formic acid aqueous solution, controlling the temperature of the water bath kettle to 15 ℃, continuously adding 2mL tertiary butyl hydroperoxide, raising the temperature in the water bath kettle to 70 ℃, reacting for 4 hours, cooling the product, precipitating, washing and drying to obtain the epoxidized ethylene propylene diene monomer;
B. Taking 8g of phenyl phosphorus dichloride, adding 5mL of toluene and 6g of anhydrous aluminum chloride, heating to 65 ℃ for reaction for 10 hours, cooling the reactant to room temperature, adding 20mL of 10wt% hydrochloric acid and 40mL of benzene for hydrolysis, separating an organic layer, extracting a water layer by using 40mL of benzene, merging the organic layers, washing by using deionized water, and evaporating the organic solvent under reduced pressure to obtain the (4-tolyl) phenyl phosphorus oxide flame retardant;
C. And adding 100mL of xylene solvent into 5g of epoxidized ethylene propylene diene monomer, fully dissolving, adding 3g of (4-tolyl) phenyl phosphorus oxide flame retardant, heating to 110 ℃, stirring for 8 hours, removing xylene by rotary evaporation after the reaction is finished, and drying in vacuum to obtain the modified ethylene propylene diene monomer.
Example 2a method for preparing a modified ethylene propylene diene monomer comprises the following steps:
A. Adding 5g ethylene propylene diene monomer into 250mL toluene solvent, placing in a water bath kettle at 50 ℃, stirring until the ethylene propylene diene monomer is completely dissolved, adding 1.8mL formic acid aqueous solution, controlling the temperature of the water bath kettle to be 30 ℃, continuously adding 2.5mL tertiary butyl hydroperoxide, raising the temperature in the water bath kettle to 80 ℃, reacting for 8 hours, cooling the product, precipitating, washing and drying to obtain the epoxidized ethylene propylene diene monomer;
B. Taking 8g of phenyl phosphorus dichloride, adding 10mL of toluene and 7g of anhydrous aluminum chloride, heating to 75 ℃ for reaction for 12 hours, cooling the reactant to room temperature, adding 25mL of 10wt% hydrochloric acid and 45mL of benzene for hydrolysis, separating an organic layer, extracting a water layer with 45mL of benzene, merging the organic layers, washing with deionized water, and evaporating the organic solvent under reduced pressure to obtain the (4-tolyl) phenyl phosphorus oxide flame retardant;
C. And adding 180mL of xylene solvent into 5g of epoxidized ethylene propylene diene monomer, fully dissolving, adding 6g of (4-tolyl) phenyl phosphorus oxide flame retardant, heating to 120 ℃, stirring for 10 hours, removing xylene by rotary evaporation after the reaction is finished, and drying in vacuum to obtain the modified ethylene propylene diene monomer.
Example 3a method for preparing a modified ethylene propylene diene monomer comprises the following steps:
A. Adding 5g ethylene propylene diene monomer into 350mL toluene solvent, placing in a water bath kettle at 60 ℃, stirring until the ethylene propylene diene monomer is completely dissolved, adding 2.5mL formic acid aqueous solution, controlling the temperature of the water bath kettle to be 35 ℃, continuously adding 5mL tertiary butyl hydroperoxide, raising the temperature in the water bath kettle to 90 ℃, reacting for 12 hours, cooling the product, precipitating, washing and drying to obtain the epoxidized ethylene propylene diene monomer;
B. Taking 8g of phenyl phosphorus dichloride, adding 10mL of toluene and 8g of anhydrous aluminum chloride, heating to 80 ℃ for reaction for 12 hours, cooling the reactant to room temperature, adding 35mL of 10wt% hydrochloric acid and 50mL of benzene for hydrolysis, separating an organic layer, extracting a water layer with 50mL of benzene, merging the organic layers, washing with deionized water, and evaporating the organic solvent under reduced pressure to obtain the (4-tolyl) phenyl phosphorus oxide flame retardant;
C. Adding 250mL of xylene solvent into 5g of epoxidized ethylene propylene diene monomer, fully dissolving, adding 8g of (4-tolyl) phenyl phosphorus oxide flame retardant, heating to 135 ℃, stirring for 12h, removing xylene by rotary evaporation after the reaction is finished, and drying in vacuum to obtain the modified ethylene propylene diene monomer.
Embodiment 4a method for preparing modified basalt fiber comprises the following steps:
(1) Soaking basalt fibers in an acetone solution for 10 hours, taking out and draining, then soaking and washing the basalt fibers in a container filled with deionized water, filtering out the basalt fibers after repeated times, and then drying the basalt fibers in an oven to obtain pretreated basalt fibers;
(2) Adding 300mL of deionized water into 2g of nano titanium dioxide, stirring and mixing at room temperature, performing ultrasonic dispersion, adding 2.4g of sodium chloroacetate, dropwise adding sodium hydroxide solution with the concentration of 0.1 mol/L to adjust the pH to 11, heating in an oil bath at 100 ℃ for 3 hours, cooling to room temperature, repeatedly washing with deionized water until the pH is neutral, and then performing centrifugal separation and drying to obtain carboxylated nano titanium dioxide;
(3) Taking 3mL of absolute ethyl alcohol, 7mL of deionized water and 90mL of gamma-aminopropyl triethoxysilane, placing the materials in a 45 ℃ for hydrolysis to obtain silane hydrolysate, then taking 10g of silane hydrolysate, adding 3g of pretreated basalt fiber and 0.05g of carboxylated nano titanium dioxide, keeping the temperature at 45 ℃ and stirring for 60min, and placing the materials in an oven for drying after the reaction is finished to obtain the modified basalt fiber.
Embodiment 5 a method for preparing modified basalt fiber comprises the following steps:
(1) Soaking basalt fibers in an acetone solution for 12 hours, taking out and draining, then soaking and washing the basalt fibers in a container filled with deionized water, filtering out the basalt fibers after repeated times, and then drying the basalt fibers in an oven to obtain pretreated basalt fibers;
(2) Adding 300mL of deionized water into 2g of nano titanium dioxide, stirring and mixing at room temperature, performing ultrasonic dispersion, adding 2.6g of sodium chloroacetate, dropwise adding sodium hydroxide solution with the concentration of 0.1 mol/L to adjust the pH to 12, heating in an oil bath at 115 ℃ for 4 hours, cooling to room temperature, repeatedly washing with deionized water until the pH is neutral, and then performing centrifugal separation and drying to obtain carboxylated nano titanium dioxide;
(3) 4mL of absolute ethyl alcohol, 6mL of deionized water and 90mL of gamma-aminopropyl triethoxysilane are taken, the mixture is put into a 50 ℃ for hydrolysis to obtain silane hydrolysate, then 3g of pretreated basalt fiber and 0.1g of carboxylated nano titanium dioxide are added into 10g of silane hydrolysate, the temperature is kept at 50 ℃ and the mixture is stirred for 40min, and the mixture is put into a baking oven for baking after the reaction is finished to obtain the modified basalt fiber.
Embodiment 6 a method for preparing a modified basalt fiber comprises the steps of:
(1) Soaking basalt fibers in an acetone solution for 12 hours, taking out and draining, then soaking and washing the basalt fibers in a container filled with deionized water, filtering out the basalt fibers after repeated times, and then drying the basalt fibers in an oven to obtain pretreated basalt fibers;
(2) Adding 300mL of deionized water into 2g of nano titanium dioxide, stirring and mixing at room temperature, performing ultrasonic dispersion, adding 3g of sodium chloroacetate, dropwise adding sodium hydroxide solution with the concentration of 0.1 mol/L to adjust the pH to 13, heating in an oil bath at 120 ℃ for 5 hours, cooling to room temperature, repeatedly washing with deionized water until the pH is neutral, and then performing centrifugal separation and drying to obtain carboxylated nano titanium dioxide;
(3) Taking 3.5mL of absolute ethyl alcohol, 6.5mL of deionized water and 90mL of gamma-aminopropyl triethoxysilane, placing the materials in a temperature of 60 ℃ for hydrolysis to obtain silane hydrolysate, then taking 10g of silane hydrolysate, adding 3g of pretreated basalt fiber and 0.15g of carboxylated nano titanium dioxide, keeping the temperature of 55 ℃ and stirring for 30min, and placing the materials in a baking oven for baking after the reaction is finished to obtain the modified basalt fiber.
Embodiment 7 is an offshore photovoltaic cable insulation sheath material, which comprises the following raw materials in parts by weight: 50 parts of high-density polyethylene, 12 parts of modified ethylene propylene diene monomer, 5 parts of modified basalt fiber, 1 part of polyethylene wax, 0.5 part of antioxidant 1010 and 0.05 part of light stabilizer 2020; wherein the modified ethylene propylene diene monomer is the modified ethylene propylene diene monomer prepared in the embodiment 1, and the modified basalt fiber is the modified basalt fiber prepared in the embodiment 4.
The preparation method of the insulating sheath material comprises the following steps: weighing the raw materials according to parts by weight, adding the high-density polyethylene, the modified ethylene propylene diene monomer, the modified basalt fiber and the lubricant into a mixer, stirring and mixing, wherein the temperature of the mixer is set to 60 ℃, the stirring time is set to 20 minutes, then adding the light stabilizer and the antioxidant, continuously stirring and mixing, and at the moment, the temperature of the mixer is set to 80 ℃, the stirring time is set to 40 minutes, so as to obtain a mixture, and putting the mixture into a double-screw extruder for extrusion molding, so as to obtain the insulating sheath material.
Embodiment 8 is an offshore photovoltaic cable insulation sheath material, which comprises the following raw materials in parts by weight: 62 parts of high-density polyethylene, 15 parts of modified ethylene propylene diene monomer, 8 parts of modified basalt fiber, 1 part of polyethylene wax, 1076 parts of antioxidant 1071 part and 0.2 part of light stabilizer 770; wherein the modified ethylene propylene diene monomer is the modified ethylene propylene diene monomer prepared in the embodiment 1, and the modified basalt fiber is the modified basalt fiber prepared in the embodiment 4.
The preparation method of the insulating sheath material is the same as that of example 7.
Embodiment 9 is an offshore photovoltaic cable insulation sheath material, which comprises the following raw materials in parts by weight: 70 parts of high-density polyethylene, 25 parts of modified ethylene propylene diene monomer, 15 parts of modified basalt fiber, 1.5 parts of oxidized polyethylene wax, 168 2 parts of antioxidant and 0.5 part of light stabilizer 944; wherein the modified ethylene propylene diene monomer is the modified ethylene propylene diene monomer prepared in the embodiment 1, and the modified basalt fiber is the modified basalt fiber prepared in the embodiment 4.
The preparation method of the insulating sheath material is the same as that of example 7.
Comparative example 1 an offshore photovoltaic cable insulation sheath material comprises the following raw materials in parts by weight: 55 parts of high-density polyethylene, 20 parts of ethylene propylene diene monomer, 11 parts of modified basalt fiber, 1 part of oxidized polyethylene wax, 2 parts of antioxidant 1010 and 0.1 part of light stabilizer 770; wherein the modified basalt fiber is the modified basalt fiber prepared in example 4.
The preparation method of the insulating sheath material is the same as that of example 7.
Comparative example 2 an offshore photovoltaic cable insulation sheath material comprises the following raw materials in parts by weight: 62 parts of high-density polyethylene, 21 parts of modified ethylene propylene diene monomer, 15 parts of basalt fiber, 1.5 parts of oxidized polyethylene wax, 1 part of antioxidant 1010 and 0.5 part of light stabilizer 770; wherein the modified ethylene propylene diene monomer is the modified ethylene propylene diene monomer prepared in example 1.
The preparation method of the insulating sheath material is the same as that of example 7.
Comparative example 3 an offshore photovoltaic cable insulation sheath material comprises the following raw materials in parts by weight: 65 parts of high-density polyethylene, 15 parts of modified ethylene propylene diene monomer, 1 part of oxidized polyethylene wax, 1 part of antioxidant 1010 and 0.2 part of light stabilizer 770; wherein the modified ethylene propylene diene monomer is the modified ethylene propylene diene monomer prepared in example 1.
The preparation method of the insulating sheath material is the same as that of example 7.
Performance detection
And (3) mechanical property detection: the mechanical properties of the insulating sheath materials prepared in examples 7 to 9 and comparative examples 1 to 3 were examined. The tensile properties were tested according to GB/T1040.2-2022 standard using a universal mechanical tester, the tensile bars were 100mm by 5mm by 3.5mm, the impact strength was tested according to GB/T1843-2008 standard, the bars were 80mm by 10mm by 4mm, and the data results were shown in Table 1.
TABLE 1 test results of mechanical Properties of samples
As can be seen from the data in Table 1, the insulating sheath materials prepared in examples 7 to 9 and comparative example 1 of the present invention have more excellent mechanical properties than those of comparative examples 2 to 3. The tensile property and impact strength of the modified basalt fiber added in the comparative example 2 are reduced, and the mechanical property of the modified basalt fiber is limited to be exerted probably due to poor bonding strength of the basalt fiber and a matrix interface, and the mechanical property of the modified basalt fiber is obviously reduced due to the fact that the basalt fiber is not added in the comparative example 3.
Salt spray resistance detection: salt spray resistance tests were carried out on the insulating sheath materials prepared in examples 7 to 9 and comparative examples 1 to 3. The salt spray test temperature was 35 ℃, the mass fraction of sodium chloride was 5%, the time was 128 hours, and the change rates of tensile strength and elongation at break were measured, and the data results were shown in Table 2.
Table 2 test results of salt spray resistance of samples
As can be seen from the data in Table 2, the insulating sheath materials prepared in examples 7 to 9 and comparative example 1 of the present invention have excellent salt spray resistance, and the change in the tensile strength and the change in the elongation at break is remarkable in comparative examples 2 and 3 without modifying basalt fiber and without adding basalt fiber.
And (3) flame retardant property detection: the insulating sheath materials prepared in examples 7 to 9 and comparative examples 1 to 3 were prepared into test samples with a specification of 100mm×6.5mm×3mm, and the flame retardant properties of the samples were evaluated with reference to the limiting oxygen index of the national standard GB/T2406.2-2009 test samples, and in general, the larger the limiting oxygen index, the better the flame retardant properties, and vice versa, and the data results were shown in Table 3.
Table 3 test results of flame retardant Properties of samples
As can be seen from the data in Table 3, the insulating sheath materials prepared in examples 7 to 9 and comparative examples 2 to 3 of the present invention have more excellent flame retardant properties than comparative example 1, because the flame retardant properties are poor due to the absence of the phosphorus-containing flame retardant by adding the unmodified ethylene propylene diene monomer in comparative example 1.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The marine photovoltaic cable insulating sheath material is characterized by comprising the following raw materials in parts by weight: 50-70 parts of high-density polyethylene, 10-25 parts of modified ethylene propylene diene monomer, 5-15 parts of modified basalt fiber, 1-1.5 parts of lubricant, 0.5-2 parts of antioxidant and 0.05-0.5 part of light stabilizer;
The modified ethylene propylene diene monomer is an epoxidized ethylene propylene diene monomer grafted (4-tolyl) phenyl phosphorus oxide flame retardant modified ethylene propylene diene monomer; the modified basalt fiber is a gamma-aminopropyl triethoxysilane and nano titanium dioxide composite modified basalt fiber.
2. The offshore photovoltaic cable insulation sheath material of claim 1, wherein the lubricant is polyethylene wax or oxidized polyethylene wax; the antioxidant is one of an antioxidant 1010, an antioxidant 1076 and an antioxidant 168; the light stabilizer is one of a light stabilizer 2020, a light stabilizer 770 and a light stabilizer 944.
3. The offshore photovoltaic cable insulation sheath material of claim 1, wherein the preparation method of the modified ethylene propylene diene monomer rubber comprises the following steps:
A. Adding ethylene propylene diene monomer into a toluene solvent, placing the ethylene propylene diene monomer into a water bath kettle at 40-60 ℃, stirring the mixture until the ethylene propylene diene monomer is completely dissolved, adding a formic acid aqueous solution, controlling the temperature of the water bath kettle to be 15-35 ℃, continuously adding tert-butyl hydroperoxide, raising the temperature in the water bath kettle to 70-90 ℃, reacting for 4-12 hours, cooling the product, precipitating, washing and drying to obtain the epoxidized ethylene propylene diene monomer;
B. Adding toluene and anhydrous aluminum chloride into phenyl phosphorus dichloride, heating to 65-80 ℃ for reaction for 10-12 hours, cooling reactants to room temperature, adding 10wt% hydrochloric acid and benzene for hydrolysis, separating an organic layer, extracting a water layer by using benzene, merging the organic layers, washing by using deionized water, and evaporating the organic solvent under reduced pressure to obtain the (4-tolyl) phenyl phosphorus oxide flame retardant;
C. And adding a dimethylbenzene solvent into the epoxidized ethylene propylene diene monomer, fully dissolving, adding a (4-tolyl) phenyl phosphorus oxide flame retardant, heating to 110-135 ℃, stirring for 8-12 hours, performing rotary evaporation to remove dimethylbenzene after the reaction is finished, and performing vacuum drying to obtain the modified ethylene propylene diene monomer.
4. The offshore photovoltaic cable insulation sheath material of claim 3, wherein the addition ratio of ethylene propylene diene monomer, formic acid aqueous solution and tert-butyl hydroperoxide in step a is 5g: 1-2.5 mL: 2-5 mL.
5. The offshore photovoltaic cable insulation sheath material of claim 3, wherein the addition ratio of phenyl phosphorus dichloride and toluene in step B is 8g: 5-10 mL.
6. The offshore photovoltaic cable insulation sheath material of claim 3, wherein the mass ratio of the epoxidized ethylene propylene diene monomer and the (4-tolyl) phenyl phosphorus oxide flame retardant in the step C is 5: 3-8.
7. The offshore photovoltaic cable insulation sheath material of claim 1, wherein the preparation method of the modified basalt fiber comprises the following steps:
(1) Soaking basalt fibers in an acetone solution for 10-12 hours, taking out and draining, then soaking and washing the basalt fibers in a container filled with deionized water, filtering out the basalt fibers after repeated for a plurality of times, and then drying the basalt fibers in an oven to obtain pretreated basalt fibers;
(2) Adding deionized water into nano titanium dioxide, stirring and mixing at room temperature, performing ultrasonic dispersion, adding sodium chloroacetate, dropwise adding sodium hydroxide solution to adjust the pH to 11-13, heating in an oil bath at 100-120 ℃ for 3-5 h, cooling to room temperature, repeatedly washing with deionized water until the pH is neutral, and performing centrifugal separation and drying to obtain carboxylated nano titanium dioxide;
(3) And (3) taking absolute ethyl alcohol, deionized water and gamma-aminopropyl triethoxysilane, hydrolyzing at 45-60 ℃ to obtain silane hydrolysate, adding pretreated basalt fiber and carboxylated nano titanium dioxide into the silane hydrolysate, keeping the temperature at 45-55 ℃ and stirring for 30-60 min, and drying in an oven after the reaction is finished to obtain the modified basalt fiber.
8. The offshore photovoltaic cable insulation sheath material of claim 7, wherein the mass ratio of nano titanium dioxide to sodium chloroacetate in step (2) is 1: 1.2-1.5.
9. The offshore photovoltaic cable insulation sheath material of claim 7, wherein the volume ratio of absolute ethyl alcohol, deionized water and gamma-aminopropyl triethoxysilane in the silane hydrolysate in the step (3) is 3-4: 6-7: 90, the mass ratio of the silane hydrolysate to the pretreated basalt fiber to the carboxylated nano titanium dioxide is 10:3:0.05 to 0.15.
10. The method for preparing the insulation sheath material for the offshore photovoltaic cable of claim 1, comprising the following steps: weighing the raw materials according to parts by weight, adding the high-density polyethylene, the modified ethylene propylene diene monomer, the modified basalt fiber and the lubricant into a mixer, stirring and mixing, wherein the temperature of the mixer is set to be 50-60 ℃, the stirring time is 15-20 min, then adding the light stabilizer and the antioxidant, continuously stirring and mixing, and at the moment, the temperature of the mixer is set to be 70-80 ℃ and the stirring time is 30-40 min to obtain a mixture, and putting the mixture into a double-screw extruder for extrusion molding to obtain the insulating sheath material.
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